Octahedral Mn(II) and Cu(II) di-tert-butylphosphate (L) complexes [ML2(imz)(4)] have been synthesized and characterized using IR, UV-vis, luminescence, and EPR spectroscopy and single crystal X-ray diffraction studies. Thermal decomposition of both the complexes (probed by TGA, DTA, and DSC) indicate stepwise elimination of iso-butene. imidazole and water to finally yield the respective ceramic materials Mn(PO3)(2) or Cu(PO3)(2).